CN1111165C - Aldehyde acetal modified quaternary phosphate and its preparing method and use - Google Patents
Aldehyde acetal modified quaternary phosphate and its preparing method and use Download PDFInfo
- Publication number
- CN1111165C CN1111165C CN00112277A CN00112277A CN1111165C CN 1111165 C CN1111165 C CN 1111165C CN 00112277 A CN00112277 A CN 00112277A CN 00112277 A CN00112277 A CN 00112277A CN 1111165 C CN1111165 C CN 1111165C
- Authority
- CN
- China
- Prior art keywords
- och
- alkyl
- modified quaternary
- hso
- roch
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention relates to germicide quaternary phosphonium salts as acetal group modified quaternary phosphonium salts, preparation methods of the germicide quaternary phosphonium salts, the application of the germicide quaternary phosphonium salts as surface active agents to sterilization and slime stripping in water injection at oil fields and industrial water treatment, and the application of the germicide quaternary phosphonium salts as germicides, emulsifying agents, antistatic agents and dispersing agents in textile industry, dyeing and printing industry and daily chemical industry.
Description
The invention belongs to the new type bactericide class, specifically a kind of aldehyde acetal modified De quaternary alkylphosphonium salt and its production and use.
The bacterium algae is more and more serious to the influence of industrial and agricultural production, particularly oil production and industrial circulating cooling water system, and the sulfatereducting bacteria that contains in oil-field flooding (Sulfate Reducing Bacteria is called for short SRB) number can reach 10
4More than/the mL, very serious to the corrosion of oil field equipment, cause will changing once in discontented 3 or four years.In industrial circulating cooling water system, there is serious bacterium algae etching problem equally.And crude oil yield, quality also seriously influenced.The easiest and the effective means that prevents SRB bacterial corrosion is to recycle to add sterilant in the water.Sterilant commonly used is quaternary ammonium salt surface active agent dodecyl benzyl dimethyl ammonium chloride (being commonly called as 1227) in oil field water and industrial circulating cooling water at present, but because life-time service makes bacterium produce resistance, drug effect is constantly descended, injected volume continues to increase, productive expense rises year by year, and causes the pollution to environment.Therefore the sterilant of studying new and effective practicality has just become state's problem to be solved of having to go to the toilet.
CN1163885A has announced a kind of modified quaternary ammonium salt class (Modified Quantery Ammonium is called for short MQA), is used for the sterilizing use of oil field water and industrial circulating cooling water sulfatereducting bacteria and anerobe.US3281365 has announced that a class is new and effective, wide spectrum, low toxicity quaternary alkylphosphonium salt sterilant [RP (R
1) (R
2) (R
3) X, R=C
6Above alkyl, R
1, R
2, R
3=C
1～C
12Alkyl, aralkyl, alkaryl, X=Cl, Br, I].This series bactericidal agent not only sterilization effect is good, but also has good foundry loam stripping performance.This series bactericidal agent commonly used at present is tetradecyl tributyl ammonium chloride (trade names is B-350).
The objective of the invention is to develop a novel modified quaternary phosphine salt sterilant, overcome the resistance of SRB existing sterilant product.
Purpose of the present invention can reach by following measure:
The sterilant of the present invention's development is that chain alkyl replaces with alkoxyl group on quaternary alkylphosphonium salt.Because the electronegativity of oxygen is bigger, makes that the positive polarity of quaternary alkylphosphonium salt is stronger, and the bacterium algae is surperficial electronegative, so the easier attack bacteria molecule of novel quaternary alkylphosphonium salt of the present invention, has better sterilization effect.Its synthetic route of bactericidal agent modified quaternary phosphine salt of the present invention is as follows respectively:
The first step: with Fatty Alcohol(C12-C14 and C12-C18) (ROH), Paraformaldehyde 96 [(CH
2O)
n], XCH
2CH
2OH 40～100 ℃ of reactions down, gets intermediate ROCH under acid (sulfuric acid, hydrochloric acid or phosphoric acid etc.) catalysis
2OCH
2CH
2X, wherein R=C
1～C
22Alkyl, n=1～1000, X=Cl, Br, HSO
4, mol ratio is a Fatty Alcohol(C12-C14 and C12-C18): Paraformaldehyde 96: HOCH
2CH
2X=1: (1～2): (1～1.5).
Second step was with tertiary phosphine P (R
1) (R
2) (R
3) with above-mentioned intermediate with mol ratio 1: (1.0～1.5) feed intake, under 60～200 ℃, protection of inert gas, 0～1MPa pressure, reacted 4～80 hours, ethylidene ether modification quaternary alkylphosphonium salt ROCH
2OCH
2CH
2P (R
1) (R
2) (R
3) X, wherein R=C
1～C
22Alkyl, R
1, R
2, R
3=C
1～C
4Alkyl, phenyl, benzyl, X=Cl, Br, HSO
4 R=C
1～C
22Alkyl, R
1, R
2, R
3=C
1～C
4Alkyl, phenyl, benzyl, X=Cl, Br, HSO
4Aldehyde acetal modified quaternary alkylphosphonium salt ROCH
2OCH
2CH
2P (R
1) (R
2) (R
3) X (R=C wherein
1～C
22Alkyl, R
1, R
2, R
3=C
1～C
4Alkyl, phenyl, benzyl, X=Cl, Br, HSO
4) be used for oil-field flooding as tensio-active agent, the sterilizing use of the sulfatereducting bacteria in the Treatment of Industrial Water, and in the purposes of the dispersion agent of the industry of textile printing and dyeing, daily-use chemical industry, emulsifying agent, static inhibitor, sterilant.
Above modified quaternary phosphine salt synthetic route is simple, and raw material is easy to get, and cost is low, the yield height, and institute's synthetic modified quaternary phosphine salt all has surfactivity and bactericidal property preferably.Adopt the SY5329-88 standard detection to the SRB sterilizing rate all 100% (bacteriocidal concentration is 20mg/L).Therefore, be widely used in oil field and Treatment of Industrial Water, weaving, washing composition, daily-use chemical industry industry as sterilant, emulsifying agent, dispersion agent, therefore the development and application of modified quaternary phosphine salt of the present invention has bigger social benefit and economic benefit.
Embodiment:
1. intermediate 2-(dodecyloxy methoxyl group) monochloroethane is synthetic
Add 0.1mol lauryl alcohol, 0.2mol Paraformaldehyde 96, catalyst sulfuric acid and solvent in four-necked bottle, stir down in 60～80 ℃ and slowly drip the 0.12mol chloroethanol, back flow reaction 3 hours is till anhydrous the telling.With the sodium bicarbonate neutralization, remove solvent, underpressure distillation gets 2-(dodecyloxy methyl) monochloroethane C
12H
25OCH
2OCH
2CH
2Cl, productive rate are 68%.
The synthesis condition of part intermediate and the results are shown in Table 1.
2. synthesizing of aldehyde acetal modified Ji quaternary alkylphosphonium salt
Add 0.5mol at reactor and press example 1 method synthetic intermediate C
12H
25OCH
2OCH
2CH
2Cl and tributylphosphine, under nitrogen protection, 100～160 ℃ of temperature controls, stirring reaction 48 hours, cooling, discharging gets the aldehyde acetal modified quaternary alkylphosphonium salt C of wax shape
12H
25OCH
2OCH
2CH
2P (C
4H
9)
3Cl, yield 98%.
The synthesis condition of the aldehyde acetal modified quaternary alkylphosphonium salt product of part and the results are shown in Table 2.
Table 1 part intermediate 2-alkoxyl group methoxy base replaces ethane
(ROCH
2OCH
2CH
2X) synthesis condition and sequence number product proportioning (mol ratio) thermotonus time yield as a result
ROH/CH
2O/HOCH
2CH
2X ℃ h ％
1 C
12H
25OCH
2OCH
2CH
2Cl 1∶1.5∶1.1 70 3 64
2 C
14H
29OCH
2OCH
2CH
2Cl 1∶2∶1.1 70 4 72
3 C
16H
33OCH
2OCH
2CH
2Cl 1∶1.4∶1.05 70 5 61
4 C
12H
25OCH
2OCH
2CH
2Br 1∶1.5∶1.2 65 5 68
5 C
14H
29OCH
2OCH
2CH
2Br 1∶1.8∶1.5 65 5 70
6 C
12H
25OCH
2OCH
2CH
2HSO
4 1∶1.5∶1.5 75 4 70
The synthesis condition of the aldehyde acetal modified quaternary alkylphosphonium salt of table 2 part with sequence number product proportioning (mol ratio) thermotonus time yield sterilizing rate * as a result
R
1PR
2R
3/ intermediate ℃ h % %
1 C
12H
25OCH
2OCH
2CH
2P(C
4H
9)
3Cl 1∶1.0 140 45 98 100
2 C
14H
29OCH
2OCH
2CH
2P(C
4H
9)
3Cl 1∶1.1 145 40 97 100
3 C
16H
33OCH
2OCH
2CH
2P(C
4H
9)
3Cl 1∶1.2 135 48 97 100
4 C
12H
25OCH
2OCH
2CH
2P(C
4H
9)
3Br 1∶1.05 170 20 96 100
5 C
14H
29OCH
2OCH
2CH
2P(C
4H
9)
3Br 1∶1.2 148 25 98 100
6 C
12H
25OCH
2OCH
2CH
2P (C
6H
5)
3HSO
41: 1.1 150 25 98 100
*The evaluation result of sterilizing rate is for adopting result's (concentration of sterilant is 20mg/L) of SY5329-88 standard test
Claims (3)
1. a modified quaternary phosphine salt sterilant is characterized in that aldehyde acetal modified quaternary alkylphosphonium salt, and it has following general formula: ROCH
2OCH
2CH
2P (R
1) (R
2) (R
3) X, wherein R=C
1～C
22Alkyl, R
1, R
2, R
3=C
1～C
4Alkyl, phenyl, benzyl, X=Cl, Br, HSO
4
2. the preparation method of aldehyde acetal modified quaternary alkylphosphonium salt is characterized in that the first step is Fatty Alcohol(C12-C14 and C12-C18) (ROH), Paraformaldehyde 96 [(CH
2O)
n], HOCH
2CH
2X 40～100 ℃ of reactions down, gets intermediate ROCH under acid catalysis
2OCH
2CH
2X, wherein R=C
1～C
22Alkyl, n=1～1000, X=Cl, Br, HSO
4, mol ratio is a Fatty Alcohol(C12-C14 and C12-C18): Paraformaldehyde 96: HOCH
2CH
2X=1: (1～2): (1～1.5); Second step was with tertiary phosphine P (R
1) (R
2) (R
3) with above-mentioned intermediate with mol ratio 1: (1.0～1.5) feed intake, at 60～200 ℃, 0～1MPa and protection of inert gas reaction 4～80 hours down, aldehyde acetal modified quaternary alkylphosphonium salt ROCH
2OCH
2CH
2P (R
1) (R
2) (R
3) X, wherein R=C
1～C
22Alkyl, R
1, R
2, R
3=C
1～C
4Alkyl, phenyl, benzyl, X=Cl, Br, HSO
4
3. aldehyde acetal modified quaternary alkylphosphonium salt ROCH
2OCH
2CH
2P (R
1) (R
2) (R
3) X R=C wherein
1～C
22Alkyl, R
1, R
2, R
3=C
1～C
4Alkyl, phenyl, benzyl, X=Cl, Br, HSO
4Be used for the sterilizing use of the sulfatereducting bacteria of oil-field flooding, Treatment of Industrial Water as tensio-active agent, and in the purposes of the dispersion agent of the industry of textile printing and dyeing, daily-use chemical industry, emulsifying agent, static inhibitor, sterilant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00112277A CN1111165C (en) | 2000-05-15 | 2000-05-15 | Aldehyde acetal modified quaternary phosphate and its preparing method and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00112277A CN1111165C (en) | 2000-05-15 | 2000-05-15 | Aldehyde acetal modified quaternary phosphate and its preparing method and use |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98111552A Division CN1061051C (en) | 1998-11-02 | 1998-11-02 | Bactericidal agent modified quaternary phosphine salt and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1280132A CN1280132A (en) | 2001-01-17 |
| CN1111165C true CN1111165C (en) | 2003-06-11 |
Family
ID=4582149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00112277A Expired - Fee Related CN1111165C (en) | 2000-05-15 | 2000-05-15 | Aldehyde acetal modified quaternary phosphate and its preparing method and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1111165C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1404643A4 (en) * | 2001-05-29 | 2008-05-07 | Univ Vanderbilt | Cleavable surfactants and methods of use thereof |
| CN114350729B (en) * | 2022-01-06 | 2022-12-13 | 安徽翠鸟生物技术有限公司 | Uridine diphosphate preparation process based on multi-technology fusion |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3281365A (en) * | 1963-12-23 | 1966-10-25 | Monsanto Co | Antiseptic detergent compositions |
| CN1163885A (en) * | 1997-03-07 | 1997-11-05 | 南京化工大学 | Bactericidal agent modified quaternary ammonium salt and preparing process thereof |
-
2000
- 2000-05-15 CN CN00112277A patent/CN1111165C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3281365A (en) * | 1963-12-23 | 1966-10-25 | Monsanto Co | Antiseptic detergent compositions |
| CN1163885A (en) * | 1997-03-07 | 1997-11-05 | 南京化工大学 | Bactericidal agent modified quaternary ammonium salt and preparing process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1280132A (en) | 2001-01-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3720838B1 (en) | Organic sulfonic acid salts of amino acid esters and process for their preparation | |
| EP1123271A1 (en) | Novel amine and quaternary ammonium compounds made from ketones and aldehydes, and compositions containing them | |
| DE60223194T2 (en) | Quaternary ammonium salts with a tertiary alkyl group | |
| CN1061773A (en) | The preparation of alkoxyalkanoic acids | |
| Tantawy et al. | Novel cationic surfactants based on waste frying oil for cleaning water surface from petroleum films: Synthesis, antimicrobial and surface properties | |
| BRPI0309484B1 (en) | USE OF ALCOXYLATES, ALCOXYLATE, PROCESS FOR THE PREPARATION OF THEREOF, AND, CLEANING, WETING, COATING, ADHESION, LEATHER DEMAGING OR COSMETIC FORMULATION OR PLANT PROTECTION | |
| CN1111165C (en) | Aldehyde acetal modified quaternary phosphate and its preparing method and use | |
| EP0182669A1 (en) | Quaternary Ammonium compounds | |
| CN1134145A (en) | Process for reducing levels of nitrite contaminants in amine oxide surfactants | |
| CN103270011B (en) | The preparation method of the polyglyceryl ether of fatty alcohol | |
| US5567213A (en) | Use of olefinic imines to scavenge sulfur species | |
| CN1041093C (en) | Fluorinated carboxylic acid esters of phosphonocarboxylic acids and phosphinocarboxylic acids and use thereof | |
| CN1317257C (en) | Nitrogen-containing ortho ester-based surfactant, its preparation and use | |
| CN1061051C (en) | Bactericidal agent modified quaternary phosphine salt and its preparation method | |
| US3772443A (en) | 5-bromo-5-nitro-1,3-dioxane,process and antimicrobial compositions | |
| CN101565388A (en) | Preparation method of 2-aryl propionitrile compounds | |
| CN1067375C (en) | Bactericidal agent modified quaternary ammonium salt and preparing process thereof | |
| CN1275572A (en) | Polyether modified quaternary microcosmic salt, its preparation process and use | |
| US4283561A (en) | Mixture of aldehydes resulting from hydroformylation of α-terpinene | |
| US7314951B2 (en) | Process and composition for lower toxicity quaternary ammonium compounds | |
| DE69635422T2 (en) | Aminonitrile intermediates for the preparation of 2-hydroxyethyliminodiacetic acid | |
| US4222954A (en) | Iodophore compounds | |
| JPH08198828A (en) | Production of quaternary ammonium salt | |
| CN1113943C (en) | Abietyl quaternary ammonium salt kind compound and preparation methd thereof | |
| CN1142169C (en) | Improved prep. of 3-trifluoro methyl-5-hydroxy-pyrazole phosphate derivatives in the presence of hydrosolvent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |